Manufacture of urea-formaldehyde condensation products and artificial material therefrom



Patented June .18, 1935 MANUFACTURE OF UREA-FORMALDEHYDE CONDENSATION PRODUCTS AND ARTI- FICIAL MATERIAL THEREFROM Ren Armenault, Paris, France, 'assignor of onehalf to" Fabriques de Produits de Chimie Organique de Lair-e, Societe Anonyme, Issy, France, a company of France No Drawing. Application February 18, 1932, 1se'ilal No. 593,925. In France February 23,

2 Claims.

In making urea-formaldehyde resins which are intended to be moulded at a raised temperature and under pressure, either alone or in combination with a fillingagent, it is desirable to obtain products which are very plasticand liquefy readily under the influence of heat. It has beei'rxfound that, without modifying the proportions-.-;,or the general operating method described in'tha U. S. patent application Ser. No. 411,212 filed'ljecemberv 2, 1929, it is possible to vary at will the plasticity of the materials which are to be moulded, this plasticity being dependent upon the degree of polymerization of the condensation products.

In particular, in the case of the condensation products prepared in the presence of a metallic carbonate or oxide, for example, those pre-' pared in the presence of zinc, lead, or bismuth oxide or carbonate, it has been observed that the degree of polymerization is above all a function of the temperature at which thecondensation is conducted and that, the duration of the heatingbeing the same, products made at the temperature of the water bath are more plastic than those which are made at the boiling point of the solution of urea in formaldehyde.

As a result of investigations based on the foregoing observation, it has been found that better conditions for the production of plastic masses which can easily be moulded are realized when the condensation occurs at ordinary temperature in the presence of a metallic carbonate or oxide.

When operating at ordinary temperature the solution is kept at ordinary temperature mayremain constant for some weeks, even after the excess of the metallic reagent has been removed by filtration.

It is to be noted that whilst this pH value is fixed for a given metal oxide or carbonate, it

varies according to the metal of the .group under consideration.

It has also been found that the preparation of the dimethylol compounds in a feebly acid medium does not present diificulty under these conditions and that these compounds have, even in the presence of an excess of formaldehyde, a stability such that they can be left without detriment at ordinary temperature for several weeks or even for a longer period, after which they may be converted, in the manner hereinafter indicated, into masses capable of being moulded.

When the diemthylol compounds made under the aforesaid conditions are allowed to stand until they have solidified, they have the appearance of a greasy crystalline mass which, like a wax or paramn, can be melted by mere heating on the water bath.

When it is desired to prepare a powder without addition of a filling agent, this crystalline mass may first be dried by exposure to air in order to remove adherent liquid, then suitably sub-divided and dried at a moderately raised temperature; there is thus produced a moulding powder which will yield, when subjected to a suitable temperature and pressure in presence of an acid condensing agent, objects which may be translucent or even transparent.

When it is desired to produce a powder containing a filling agent, the aforesaid crystalline mass may be melted'on the water bath andthe melt used for impregnating various filling agents, such as cellulose, hydrocellulose, powdered horn, casein, asbestos fibres or asbestos powder or the like, or mixtures of any of these agents, with or without coloured mineral filling agents. The impregnated filling agents are dried at a low temperature and ground; during the grinding operation there may be added a substance ca-, pable of accelerating the polymerization at the moulding temperature, such as an acid, an acid salt, or a salt or ester-salt capable of liberating acid. 'It is also possible to add these substances to the molten product before the impregnation of the filling agents. In the production of moulding. powders containing filling agents it is often more advantageous to impregnate the filling agents not with the dimethylol syrups, but with freshly prepared, reactive solutions of urea and formaldehyde whose pH value has been adjusted by treatment with a metal carbonate or oxide which has afterwards been separated by filtration. Under these conditions the condensation reaction occurs in the midst of the filling agent, so that the operations of mixing or of fusing the dimethylol products are avoided and complete homogeneity is ensured. After standing for about 36-48 hours, which period may be reduced if crystallization is initiated by means, for example, of some crystals or portions from a preceding operation, lit

suffices to dry the impregnated filling agents at a low temperature if desired after they have ture which might occur during crystallizatiom.

been air-dried, and then to grind them, in. order to obtain, as in the process previously described,

stable materials of high plasticity which are well sufiices to subject them to the action of heat,-

tlie degree of polymerization being then a function of the temperature or, for a given temperature, of the duration of heating.

The products, thus obtained havethe appear ance of stable syrups. They may be converted into moulding materials byusing them to impregnate various filling agents, such as cellulose, hydrocellulose, horn and so on. They may also serve, after they have been concentrated for the preparation of varnishes or of transparent or opaque masses which, when hardened in-known manner, are capable of being worked. Advantage may be taken of the intermediate stage which precedes the finalvhardening and may beprolonged at will by control of the pH value or the temperature, to sub-dividefthe products by suitable mechanical means and, to.

convert them into plates or various shaped masses or into the powders which are capable of being again agglomerated by theaction of pressureand heat.

.The following examples illustrate the invention, the parts being by weight:

Example 1.-4 parts of precipitated zinc carbonate are added to a solution of parts of urea in 400 parts of formaldehyde of 30 per cent. strength. After the whole has been stirred for 1530 minutes, it can be ascertained that the pH value of the solution has become adjusted to a value in the neighbourhood of pIfI=6.

The excess of' zinc carbonate is removed-by filtration and the solution is allowed to stand at-ordinary temperature; after 24-36 hours, the

formation of a crystalline product can be observed and finally the solution sets to a white greasy mass resembling a wax or paraflin. Crystallization may be promoted by stirring or by seeding with crystals from'a previous operation and it is possible to avoid the rise in tempera- When the crystalline mass is reheated on the water bath to a moderate temperature, it quick- "ly becomes liquid; it may be used directly or there may be added to it one part of crystallized ammonium acetate which produces an acid reaction. I

The syrup maybe used to impregnate, ior example, 100 parts of cellulose, hydrocellulose or the like; the impregnated mass is dried in a current of air at a low temperature, that is to say at a temperature which is not allowed to exceed 50-60 C., and is finally ground.

During the grinding theremay be added a substance which promotes the polymerization, for example 0,5 per cent. of benzoic acid, or a coloring matter, a, plasticizer, a stearate or the like.

Example 2.-In the preceding example the proportion of formaldehyde may be reduced to g 100 parts of formaldehyde (CHzO) for 100 parts of urea without appreciable modification of the general procedure. The relative proportions of the condensation product and the filling agent may be varied within wide limits in accordance with the properties required of the final products.

Example 3.-The crystalline methylol product of low melting. point may be dried after a preliminary drying by exposure to air. After the addition of an acid, an acid salt or an acid ester capable of promoting the polymerization, it yields unfilled powders from which there can be obtained by moulding at a raised temperature materials which are translucent or completely transparent.

Example 4.-In Examples 1 and 2, the filling agent be impregnated directly with the mixture of urea and formaldehyde immediately after its treatment. with the metal carbonate selected and removal of the excess of the latter by filtra perature for 36-48 hours; it is then dried by exposure to air, if necessary, and then dried at a moderate temperature and ground.

Example 5.-The syrup obtainedmy heating the crystalline mass for a shorter or longer period is concentrated to about half its initial weight and is then allowed to stand at a low temperature, with or without the addition of a plasticizing agent such as ethyl alcohgl benzyl-iy alcohol, triacetin or the like, until'it has solidified. The mass is then mechanically subdivided, dried'ata low temperature'and ground.

material.

Example 7.--The syrup obtained by polymerization of the crystalline mass underthe influence of heat, yields, when concentrated, a material having. a good stability and suitable as a varnish base. It may be mixed withvarious application is extended.

- The-same syrup when concentrated and cast in moulds of various shapes yields on heating at a temperature of 50-60 C. hard masses which are completely transparent and can be carved and worked with the usual tools.

solvents capable of modifying its properties, for example ethyl alcohol, methyl ,alcohol, benzyl alcohol and the like, whereby the scope of its I What I claim is: v

1. Method of producing a moldable powder which comprises agitating approximately 4 parts of precipitated zinc carbonate in an aqueous mixture of 100 parts of urea and 100-120 parts of formaldehyde, removing the undissolved zinc carbonate, allowing the reaction mixture to stand at room temperature for 24-36 hours to obtain a greasy, crystalline 'mass, drying said 10 mass, and comminuting same to give a moldable powder.

2. Method of producing a moldable powder which comprises agitating approximately 4 parts of precipitated zinc carbonate in an aqueous mixture of 100 parts of urea and 100-120 parts of formaldehyde, removing the undissolved zinc carbonate, allowing the reaction mixture to stand at room temperature for 24-36 hours to obtain a greasy, crystalline mass, melting said mass, mixing the resulting liquid with a filler, drying the mixture obtained, and comminuting same to give a moldable powder.

RENE ARMENAULT. 

